Poly(ether sulfone)s and poly(ether amide sulfone)s and methods of their preparation

ABSTRACT

Poly(ether sulfones) (PES) and poly(ether amide sulfones) (PEAS) were prepared from post-consumer polycarbonates and polyesters, respectively, using a single vessel in batch mode (all reactants present when heating was initiated). The depolymerization of the initial polymer occurs concurrently with step growth polymerization to form a product polymer having a number average molecular weight of at least 5000.

BACKGROUND

The present invention relates to poly(ether sulfone)s and poly(etheramide sulfone)s and methods of their preparation, more specifically topoly(arylene ether sulfone)s and poly(arylene ether amide sulfone)sprepared from post-consumer polycarbonates and/or polyesters.

Current methods for recycling PET involve melting the thermoplastic andreformulating new products from the melt. This process is limited as tohow many times it can be implemented because the recycling processprogressively degrades the mechanical properties of the polymer.

Depolymerization of waste plastic bottles provides an abundant source ofmonomers for new materials. Recently, a depolymerization of PETcatalyzed by a bifunctional catalyst, triazabicycloundecene (TBD), wasused to form monomer bis(hydroxyethyl terephthalate) (BHET), which canbe used to produce virgin PET. Generally, the nucleophilic agent (i.e.,ethylene glycol) is employed in superstoichiometric amounts at hightemperatures in order to achieve appreciable conversion to the desiredBHET monomer.

An ongoing need exists for more efficient methods of recyclingpolyesters and polycarbonates.

SUMMARY

Accordingly, a poly(ether amide sulfone) (PEAS) is disclosed having astructure in accordance with formula (16):

wherein

-   -   n is a positive number having an average value greater than or        equal to 1,    -   m is a positive number having an average value greater than or        equal to 1,    -   each E′ is an independent monovalent radical selected from the        group consisting of hydrogen and electron withdrawing groups,    -   each L^(a) is an independent divalent radical comprising 2 or        more carbons,    -   each L^(d) is an independent divalent radical comprising 2 or        more carbons,    -   each L′ is an independent divalent linking group comprising 1 or        more carbons,    -   Z′ is a first polymer chain end group,    -   Z″ is a second polymer chain end group, and    -   vertical stacking of the repeat units enclosed by parentheses        within the square brackets indicates a random distribution of        the repeat units in the structure of the PEAS.

Also disclosed is a method, comprising:

-   -   forming a mixture comprising        i) a polyester having a repeat unit of formula (8):

-   -   wherein        -   L′ is a divalent radical comprising 1 or more carbons, and        -   L″ is a divalent radical comprising 2 or more carbons,            ii) an amino-alcohol of formula (10):            HO-L^(d)-NH₂  (10),    -   wherein        -   L^(d) is a divalent radical comprising 2 or more carbons,            iii) a bis-aryl sulfone of formula (4):

-   -   wherein

each E′ is an independent monovalent radical selected from the groupconsisting of hydrogen and electron withdrawing groups, and

each X′ is an independent monovalent leaving group,

iv) a diol compound of formula (1),HO-L^(a)-OH  (1),

-   -   wherein        -   L^(a) is a divalent radical comprising 2 or more carbons,            v) a base, and            vi) a solvent; and    -   heating the mixture at a reaction temperature of about 150° C.        to about 250° C., wherein the diol compound is substantially        non-volatile at the reaction temperature, thereby forming a        poly(ether amide sulfone) (PEAS).

Another method is disclosed, comprising:

-   -   forming a mixture comprising        i) a polycarbonate having a repeat unit of formula (2):

-   -   wherein        -   L^(b) is a divalent radical comprising 2 or more carbons,            ii) a bis-aryl sulfone of formula (4):

-   -   wherein

each E′ is an independent monovalent radical selected from the groupconsisting of hydrogen and electron withdrawing groups, and

each X′ is an independent monovalent leaving group,

iii) a base, and

iv) a solvent; and

-   -   heating the mixture at a reaction temperature of about 150° C.        to about 250° C., thereby forming a poly(ether sulfone) (PES).

Also disclosed are molding compositions comprising an above-describedpolymer and one or more optional additives.

Further disclosed is a method, comprising:

-   -   forming a mixture comprising        i) an ester material comprising two ester groups,        ii) an amino-alcohol of formula (10):        HO-L^(d)-NH₂  (10),    -   wherein    -   L^(d) is a divalent radical comprising 2 or more carbons,        iii) a bis-aryl sulfone of formula (4):

-   -   wherein    -   each E′ is an independent monovalent radical selected from the        group consisting of hydrogen and electron withdrawing groups,        and    -   each X′ is an independent monovalent leaving group,        iv) a diol compound of formula (1),        HO-L^(a)-OH  (1),    -   wherein    -   L^(a) is a divalent radical comprising 2 or more carbons,        v) a base, and        vi) a solvent; and    -   heating the mixture at a reaction temperature of about 150° C.        to about 250° C., wherein the diol compound is substantially        non-volatile at the reaction temperature, thereby forming a        poly(ether amide sulfone) (PEAS).

The above-described and other features and advantages of the presentinvention will be appreciated and understood by those skilled in the artfrom the following detailed description, drawings, and appended claims.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a ¹H NMR spectrum of P-1 prepared from dimethyl terephthalate(DMT) and tyramine (Tyr, Example 1).

FIG. 2 is a ¹H NMR spectrum of P-1 prepared from polyester PBT and Tyr(Example 2).

FIG. 3 is a ¹H NMR spectrum of P-2 prepared from polycarbonate PC-1(Example 3).

FIG. 4 is a ¹H NMR spectrum of the crude product formed in Example 6.

FIG. 5 is a ¹H NMR spectrum of the purified product formed in Example 6.

FIG. 6 is a ¹H NMR spectrum of the crude product formed in Example 7.

FIG. 7 is a ¹H NMR spectrum of the purified product formed in Example 7.

FIG. 8 is a ¹H NMR spectrum of the reaction mixture of Example 8 after2.5 hours, showing the presence of compound I-1.

FIG. 9 is a ¹³C NMR spectrum of P-8 formed in Example 8.

FIG. 10 is a ¹H NMR spectrum of P-8 formed in Example 8.

FIG. 11 is a gel permeation chromatography trace of the purifiedpoly(arylene ether amide sulfone) formed in Example 8, having 30% amideincorporation.

FIG. 12 is a ¹H NMR spectrum of purified N₁,N₄-bis(4-hydroxyphenyl)terephthalamide monomer (I-1) prepared in Example 9.

FIG. 13 is a ¹H NMR spectrum of the polymer P-8 prepared in Example 10using pre-formed I-1 prepared in Example 9.

DETAILED DESCRIPTION

Disclosed are methods of forming poly(ether sulfone)s (PES) by a stepgrowth polymerization starting from a carbonate material comprising twoor more carbonate groups. The step growth polymerizations are conductedusing a single vessel containing two or more polymerizable reactants. Inan embodiment, one of the reactants is a polycarbonate that undergoes adepolymerization during the step growth polymerization.

Also disclosed are methods of forming poly(ether amide sulfone)s (PEAS)by a step growth polymerization starting from an ester materialcomprising two or more ester groups. The polymerizations are conductedusing a single vessel containing four or more polymerizable reactants.In an embodiment, one of the reactants is a polyester that undergoes adepolymerization during the step growth polymerization. The formation ofthe PEAS involves concurrent formation of ether and amide linkages ofthe PEAS backbone.

The PES and/or PEAS product of the step growth polymerizations can havea number average molecular weight (Mn) of about 5,000 to about1,000,000.

The ester material comprises two or more ester groups. These includecompounds (e.g., dimethyl terephthalate), polyesters, and combinationsthereof.

The carbonate material comprise two or more carbonate groups. Theseinclude compounds comprising two or more carbonate groups,polycarbonates, and combinations thereof.

Herein, polyesters and polycarbonates that are used as startingmaterials for the disclosed methods are also referred to as initialpolymers. The initial polymer can be a first generation polymer(pre-consumer use) and/or a recycle polymer (post-consumer use). In anembodiment, the initial polymer is a post-consumer polymer.

In the following discussion, reference will be made to diol compounds(diols) and dioxy fragments of diol compounds. As an illustration, adiol compound can have a structure according to formula (1):HO-L^(a)-OH  (1),wherein L^(a) is a divalent radical comprising 2 or more carbons. Thedioxy fragment of a diol compound of formula (1) is *—O-L^(a)-O—*. As amore specific example, the dioxy fragment of ethylene glycol(HO—CH₂CH₂—OH) is (*—O—CH₂CH₂—O—*). Herein, starred bonds representattachment points, not methyl groups.

Exemplary non-limiting diol compounds include ethylene glycol, propyleneglycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol,1,12-dodecanediol, 2-ethyl-1,10-decanediol, 2-butene-1,4-diol,1,3-cyclopentanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol,1,3-cyclopentanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol,1,4-bis(hydroxymethyl)benzene, resorcinol, 4-bromoresorcinol,hydroquinone, 4,4′-dihydroxybiphenyl, 1,6-dihydroxynaphthalene,2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane,bis(4-hydroxyphenyl)difluoromethane,bis(4-hydroxyphenyl)diphenylmethane,bis(4-hydroxyphenyl)-1-naphthylmethane, 1,1-bis(4-hydroxyphenyl)ethane,1,2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane,2,2-bis(4-hydroxyphenyl)propane (“bisphenol A”),2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)isobutane,1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)cyclododecane,trans-2,3-bis(4-hydroxyphenyl)-2-butene,2,2-bis(4-hydroxyphenyl)adamantane,2,2-bis(4-hydroxyphenyl)acetonitrile,2,2-bis(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3-ethyl-4-hydroxyphenyl)propane,2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,2,2-bis(3-allyl-4-hydroxyphenyl)propane,2,2-bis(3-methoxy-4-hydroxyphenyl)propane,2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane,2,2-bis(2,3,5,6-tetramethyl-4-hydroxyphenyl)propane,2,2-bis(3-5-dichloro-4-hydroxyphenyl)propane,2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane,2,2-bis(2,6-dibromo-3,5-dimethyl-4-hydroxyphenyl)propane, a,a-bis(4-hydroxyphenyl)toluene,α,α,α′,α′-tetramethyl-α,α′-bis(4-hydroxyphenyl)-p-xylene,2,2-bis(4-hydroxyphenyl)hexafluoropropane,1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene,4,4′-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycolbis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) ether,bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide,bis(4-hydroxyphenyl) sulfone, bis(3,5-dimethyl-4-hydroxyphenyl) sulfone,9,9-bis(4-hydroxyphenyl)fluorene, 2,7-dihydroxypyrene,3,3-bis(4-hydroxyphenyl)phthalide, 2,6-dihydroxydibenzo-p-dioxin,2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathiin,2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran,3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole.

Poly(ether sulfone) (PES)

The reaction mixture for preparing a PES comprises a carbonate materialcomprising two or more carbonate groups, a bis-aryl sulfone, a base, anda solvent.

It should be understood that the carbonate material can be usedsingularly or in combination with one or more other carbonate materials,the bis-aryl sulfone can be used singularly or in combination with oneor more other bis-aryl sulfones, the base can be used singularly or incombination with one or more other bases, and the solvent can be usedsingularly or in combination with one or more other solvents.

The reaction mixture to form a PES comprises the carbonate material andthe bis-aryl sulfone in a molar ratio of about 1:1. When the carbonatematerial is a polymer, the amount of carbonate material can be based onthe number average molecular weight (Mn) of the polymer.

The reaction mixture to form a PES comprises the base in an amount ofabout 1.05 molar equivalents relative to the bis-aryl sulfone.

The reaction mixture to form a PES is performed using a total solidsconcentration of about 15 wt % to about 25 wt % based on total weight ofthe reaction mixture.

Non-limiting examples of carbonate compounds comprising two carbonategroups include of catechol, resorcinol, hydroquinone,4,4′-bis(hydroxyphenyl)methane, and bisphenol A. Non-limiting examplesof dialkyl and diaryl dicarbonates of bisphenol A include:

(bisphenol A dimethyl dicarbonate), and

(bisphenol A diphenyl dicarbonate).

The carbonate material can be a polycarbonate. Non-limiting exemplarypolycarbonates include those having a repeat unit represented by formula(2):

wherein L^(b) is a divalent radical comprising 2 or more carbons.

Non-limiting polycarbonates include those having a structure representedby formula (3):

wherein

-   -   n is a positive number having an average value greater than 1,    -   L^(b) is a divalent radical comprising 2 or more carbons,    -   U′ is a first polymer chain end group, and    -   U″ is a second polymer chain end group.

The fragment *—O-L^(b)-O—* of formula (2) is a dioxy fragment of a diolcompound HO-L^(b)-OH. In a preferred embodiment, L^(b) comprises atleast one aromatic ring linked to at least one of the hydroxy groups.

A more specific polycarbonate is poly(bisphenol A carbonate) (PC-1),which has a structure:

wherein

-   -   n is a positive number having an average value greater than 1,    -   U′ is a first polymer chain end group, and    -   U″ is a second polymer chain end group.

In this example, the moiety

is a dioxy fragment of bisphenol A.

In an embodiment, the polycarbonate is a post-consumer poly(bisphenol Acarbonate).

First and second end groups U′ and U″ of the polycarbonate can be anysuitable end group, providing the end group does not adversely affectthe formation of the PES. In an embodiment U′ is

and U″ is hydrogen.

The bis-aryl sulfone for forming a PES has a structure according toformula (4):

wherein

each E′ is an independent monovalent radical selected from the groupconsisting of hydrogen and electron withdrawing groups, and

each X′ is an independent monovalent leaving group.

Exemplary non-limiting electron withdrawing groups include nitro(*—NO₂), cyano (*—CN), trifluoromethyl (*—CF₃), trichloromethyl(*—CCl₃), and alkylsulfones (*—S(═O)₂R^(a)), wherein R^(a) is an alkylor aryl group comprising 1 to 10 carbons), and combinations thereof.

Exemplary non-limiting leaving groups include fluoride, chloride,bromide, iodide, trifluoromethoxy (*—OCF₃), trichloromethoxy (*—OCCl₃),and trifluoromethanesulfonyl (*—OS(═O)₂CF₃).

Exemplary non-limiting bases for forming a PES include alkyl ammoniumhydroxides, alkyl ammonium carbonates, alkyl ammonium biscarbonates,alkylammonium borates, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN),1,6-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane(DABCO), 1,5,7-triaza-bicyclo[4.4.0]dec-5-ene (TBD),dimethylaminopyridine (DMAP), pyridine, trialkylamines, alkylammoniumfluorides, (e.g., tetraalkylammonium fluorides), metal ion hydroxides,metal ion carbonates, and ammonium hydroxide. More specific metal ionhydroxides include alkali metal ion hydroxides and alkaline earth metalion hydroxides. More specific metal ion carbonates include alkali metalion carbonates and alkaline earth metal ion carbonates, including thoseof lithium ion, sodium ion, potassium ion, rubidium ion, and/or cesiumion. Useful alkaline earth metal ion hydroxides include those ofmagnesium ion, calcium ion, and/or barium ion. The hydrated form of thebase can be used. The bases can be used singularly or in combination. Inan embodiment the base comprises a carbonate group. In anotherembodiment, the base is potassium carbonate (K₂CO₃). The base can beused in an amount of about 0.05 to about 1.1 molar equivalents relativeto the diaryl sulfone.

The solvent for forming a PES is preferably a polar aprotic solvent.Exemplary non-limiting polar aprotic solvents include dimethylformamide(DMF), dimethyl acetamide (DMA), dimethyl sulfoxide (DMSO), N-methylpyrollidinone (NMP), N-cyclohexyl pyrollidinone (CHP),1,3-dimethyl-2-imidazolidinone, hexamethyl phosphoramide (HMPA),hexamethyl phosphorous triamide (HMPT), tributyl phosphate, tricresylphosphate (TCP), triphenyl phosphate (TPP), tributyl phosphate (TBP),N-(n-butyl) benzene sulfonamide, and N-ethyl toluene sulfonamide. In anembodiment, the solvent is N-cyclohexyl pyrollidinone (CHP).

The reaction mixture is heated at a temperature of about 150° C. toabout 250° C. for about 1 hour to about 48 hours, thereby forming thePES. Preferably, the reaction is conducted using a stream of inert gas(e.g., nitrogen) to remove any volatile organic byproducts during thestep growth polymerization. Consumption of the starting materials can bemonitored using any suitable technique (e.g., proton nuclear magneticresonance (′H NMR), infrared spectroscopy). Thus, the PES can be formedin a single pot and in a single step. The PES can be isolated and/orfurther purified as necessary using known techniques (e.g.,precipitation).

In a particular embodiment, the base comprises a carbonate group havinga charge of −2 and the base is used in an amount of 1.0 to 1.1 molarequivalents relative to the diaryl sulfone. The carbonate dianion (CO₃⁻²) reacts with the backbone carbonyl group of the carbonate material,releasing carbon dioxide and an intermediate bis-alkoxide. Thebis-alkoxide then undergoes a step growth polymerization with the diarylsulfone to form the PES.

The PES has a structure in accordance with formula (5):

wherein

-   -   m is a positive number greater having an average value greater        than 1,    -   each L^(b) is an independent divalent linking group comprising 2        or more carbons,    -   each E′ is an independent monovalent radical selected from the        group consisting of hydrogen and electron withdrawing groups,    -   Y′ is a first polymer chain end group, and    -   Y″ is a second polymer chain end group.

Y′ and Y″ can be any suitable end group. As a non-limiting example, Y′can be hydrogen and Y″ can be an *—O-L^(b)-OH group (i.e., a residue ofthe diol portion of the initial polycarbonate). As another non-limitingexample, Y′ can be the bis-aryl sulfone residue:

wherein X′ is a leaving group and each E′ is an electron withdrawinggroup, and Y″ can be an above-described leaving group X′ of the bis-arylsulfone.

Each L^(b) of the PES can be an alkylene or an arylene group. When L^(b)of the dioxy fragment *—O-L^(b)-O—* comprises an aromatic ring, thepoly(ether sulfone) is referred to herein as a poly(arylene ethersulfone) (PAES). In an embodiment, L^(b) comprises at least one aromaticring. In another embodiment, *—O-L^(b)-O—* is a dioxy fragment ofbisphenol A.

More specific poly(arylene ether sulfone)s have a structure inaccordance with formula (6):

wherein

-   -   m is a positive number having an average value greater than or        equal to 1,    -   R′ is a monovalent radical selected from the group consisting of        hydrogen, halides, and groups comprising 1 or more carbons,    -   R″ is a monovalent radical selected from the group consisting of        hydrogen, halides, and groups comprising 1 or more carbons,    -   each E′ is an independent monovalent radical selected from the        group consisting of hydrogen and electron withdrawing groups,    -   Y′ is a first polymer chain end group, and    -   Y″ is a second polymer chain end group.

In an embodiment, each E′ is hydrogen. In another embodiment, R′ ismethyl and R″ is methyl. In another embodiment, R′ is trifluoromethyland R″ is trifluoromethyl. In another embodiment, R′ is fluoride and R″is fluoride. In another embodiment, Y′ is hydrogen and Y″ has astructure according to formula (7):

wherein

-   -   R′ is a monovalent radical selected from the group consisting of        hydrogen, halides, and groups comprising 1 or more carbons, and    -   R″ is a monovalent radical selected from the group consisting of        hydrogen, halides, and groups comprising 1 or more carbons.

The PES can have a number average molecular weight (Mn) of about 1000 toabout 1,000,000, more specifically 1000 to about 100,000.

Poly(Ether Amide Sulfone) (PEAS)

The reaction mixture for preparing a poly(ether amide sulfone) (PEAS)comprises an ester material comprising two or more ester groups, anamino-alcohol compound comprising a one primary amine group and onehydroxy group, a bis-aryl sulfone, a diol compound that is substantiallynon-volatile at the reaction temperature, a base, and a solvent. Thebis-aryl sulfone, the diol compound, the base, and the solvent can be anabove-described bis-aryl sulfone, an above-described diol compound offormula (1), an above-described base, and an above-described solvent,respectively. It should be understood that the ester material,amino-alcohol, bis-aryl sulfone, diol compound, base, and solvent can beused singularly or in combination with one or more other respectiveester materials, amino-alcohols, bis-aryl sulfones, diol compounds,bases, and solvents.

The reaction mixture for forming a PEAS comprises the ester material,the amino-alcohol, the diol compound, and the bis-aryl sulfone in amolar ratio of about 0.5:1.0:0.5:1.0, respectively. When the estermaterial is a polyester, the amount of polyester can be based on numberaverage molecular weight (Mn) of the polyester.

The reaction mixture for forming a PEAS comprises the base in an amountof about 1.05 molar equivalents relative to bis-aryl sulfone.

The reaction mixture for forming a PEAS is conducted using a totalsolids concentration of about 15 wt % to about 25 wt % based on totalweight of the reaction mixture.

Non-limiting examples of ester materials comprising two ester groupsinclude dimethyl terephthalate (DMT), dimethyl phthalate (DMP), dimethylisophthalate, bis(2-hydroxyethyl) terephthalate, combinations of theforegoing, and the like.

The ester material can be a polyester. Non-limiting exemplary polyestersinclude those having a repeat unit represented by formula (8):

wherein

-   -   L′ is a divalent radical comprising 1 or more carbons, and    -   L″ is a divalent radical comprising 2 or more carbons.

Non-limiting polyesters include those having a structure represented byformula (9):

wherein

-   -   m is a positive number having an average value greater than 1,    -   W′ is a first polymer chain end group,    -   W″ is a second polymer chain end group,    -   L′ is a divalent radical comprising 1 or more carbons, and    -   L″ is a divalent radical comprising 2 or more carbons.

First and second end groups W′ and W″ of the polyester can be anysuitable end groups, providing the end groups do not adversely affectthe formation of the PEAS.

Preferably, L′ comprises at least one aromatic ring and L″ is analkylene group comprising 2-4 carbons. For example, L″ can be anethylene group (*—CH₂CH₂—*) and/or a 1,4-butylene group(*—CH₂CH₂CH₂CH₂—*). Even more preferably, L′ is phenylene and *—O-L″-O—*is a dioxy fragment of ethylene glycol and/or 1,4-butane diol. In apreferred embodiment, the polyester is selected from the groupconsisting of poly(ethylene terephthalate) (PET), poly(butyleneterephthalate) (PBT)), and combinations thereof

The reaction mixture to form a PEAS comprises an amino-alcohol. Theamino-alcohol can have a structure according to formula (10):HO-L^(d)-NH₂  (10),wherein L^(d) is a divalent radical comprising 2 or more carbons.

More specific amino-alcohols have a structure according to formula (11):HO-L^(e)-CH₂—NH₂  (11),wherein L^(e) a divalent radical comprising 1 or more carbons. In anembodiment, L^(e) comprises an aromatic ring.

More specific amino-alcohols have a structure according to formula (12):

wherein

-   -   j′ is an integer having a value of 0 to 4,    -   k′ is an integer having a value of 0 or more, and    -   each C′ is an independent monovalent radical selected from the        group consisting of halides and substituents comprising 1 or        more carbons.

It should be understood that each carbon labeled 2, 3, 5 and 6 of thearomatic ring of formula (12) is linked to hydrogen when not bound to aC′ group.

An even more specific amino-alcohol is tyramine (Tyr):

The reaction mixture to form a PEAS comprises a diol compound of formula(1), HO-L^(a)-OH, which is substantially non-volatile at the reactiontemperature used to form the PEAS. Preferably, the diol compoundcomprises at least one aromatic alcohol. The diol compound can be anabove-named diol compound. Poly(ether amide sulfone)s prepared fromaromatic diol compounds are also referred to herein as poly(aryleneether amide sulfone)s (PAEAS).

Preferably, the diol compound has a structure according to formula (13):

wherein

-   -   R′ is a monovalent radical selected from the group consisting of        hydrogen, halides and groups comprising 1 or more carbons, and    -   R″ is a monovalent radical selected from the group consisting of        hydrogen, halides and groups comprising 1 or more carbons.

R′ and R″ can together complete a ring that includes carbon labeled 1.

In an embodiment, R′ is methyl and R″ is methyl (bisphenol A, (BPA)).

The reaction mixture comprising the ester material, amino-alcohol, diolcompound, bis-aryl sulfone, base, and solvent is heated at a temperatureof about 150° C. to about 250° C. for about 1 hour to about 48 hours,thereby forming a PEAS. Preferably, the reaction is conducted using astream of inert gas (e.g., nitrogen) to remove volatile organicbyproducts such as ethylene glycol (boiling point (BP)=197° C.) and1,4-butanediol (BP=235° C.) during the step growth polymerization.Preferably, the diol compound of the PEAS reaction mixture issubstantially non-volatile at the reaction temperature, and therefore isnot removed by the inert gas stream. Consumption of the startingmaterials can be monitored using any suitable technique (e.g., protonnuclear magnetic resonance (′H NMR), infrared spectroscopy).

The primary amine group of the amino-alcohol compound selectivelydepolymerizes a polyester (PET and/or PBT), thereby releasing a volatilediol compound (e.g., ethylene glycol and/or butylene glycol,respectively) and generating a diol-diamide intermediate. The volatilediol can be removed by the inert gas stream and subsequently isolated bycondensation for recycling purposes.

The diol-diamide intermediate has a structure according to formula (14):

wherein

-   -   L′ is a divalent radical comprising 1 or more carbons, and    -   each L^(d) is an independent divalent radical comprising 2 or        more carbons.

More specific diol-diamide intermediates have a structure according toformula (15):

wherein

-   -   each L^(d) is an independent divalent radical comprising 2 or        more carbons.

In a second reaction, which can occur concurrently or subsequently toformation of the diol-diamide intermediate, alcohol groups of thenon-volatile diol and diol-diamide selectively undergo a nucleophilicsubstitution reaction with bis-aryl sulfone, thereby forming apoly(ether amide sulfone) (PEAS). Thus, the PEAS can be formed in asingle vessel and in a single heating step. The PEAS can be isolatedand/or further purified as necessary using known techniques (e.g.,precipitation).

The poly(arylene ether amide sulfone) (PEAS) has a structure inaccordance with formula (16):

wherein

-   -   n is a positive number having an average value greater than or        equal to 1,    -   m is a positive number having an average value greater than or        equal to 1,    -   each E′ is an independent monovalent radical selected from the        group consisting of hydrogen and electron withdrawing groups,    -   each L^(a) is an independent divalent radical comprising 2 or        more carbons,    -   each L^(d) is an independent divalent radical comprising 2 or        more carbons,    -   each L′ is an independent divalent linking group comprising 1 or        more carbons,    -   Z′ is a first polymer chain end group, and    -   Z″ is a second polymer chain end group.

In the above notation, vertical stacking within the square bracketsindicates a random distribution of the repeat units enclosed by theparentheses. Subscripts m and n represent average numbers of the repeatunits, respectively. End groups Z′ and Z″ can be linked to any one ofthe vertically stacked repeat units.

More specific poly(ether amide sulfone)s are poly(arylene ether amidesulfone)s (PAEAS) having a structure in accordance with formula (17):

wherein

-   -   n is a positive number greater than or equal to 1,    -   m is a positive number greater than or equal to 1,    -   each R′ is an independent monovalent radical selected from the        group consisting of hydrogen and groups comprising 1 or more        carbons,    -   each R″ is an independent monovalent radical selected from the        group consisting of hydrogen and groups comprising 1 or more        carbons,    -   each E′ is an independent monovalent radical selected from the        group consisting of hydrogen and electron withdrawing groups,    -   each L′ is an independent divalent linking group comprising 1 or        more carbons,    -   each L^(e) is an independent divalent linking group comprising 1        or more carbons,    -   Z′ is a first polymer chain end group, and    -   Z″ is a second polymer chain end group.

Non-limiting first end groups Z′ include hydrogen, and groups comprisingat least one carbon.

Non-limiting second end groups Z″ include leaving groups X′ of thediaryl sulfone and groups comprising at least one carbon.

The PEAS can have a number average molecular weight (Mn) of about 5000to about 1,000,000, more specifically 5,000 to about 50,000.

Commercial Utility

Poly(arylene ether sulfone)s, including the commercially availablepolysulfones, poly(ether sulfone)s, poly(ether ether sulfone)s andpoly(biphenyl ether sulfone)s have been valued for years because oftheir excellent thermal stability, along with their high tensilestrength, outstanding toughness, high dimensional stability, high heatdeflection temperature, inherent flame retardancy (combustion resistancewithout additives), and good environmental stress cracking resistance.Accordingly, poly(arylene ether sulfone)s have found application innumerous applications including electrical and electronic componentssuch as connectors, sockets and trays, aircraft components such asinterior panels and bags, pipe fittings and manifolds for plastic pipingsystems, and even friction-and-wear resistant components such asbushings, thrust washers, bearings, slides and gears.

Potential industrial applications include molding compositions, whichcan comprise the any of the above-described sulfone polymers and one ormore optional additives. Additives include but are not limited to dyes,pigments, reinforcing agents, antioxidants, mold release agents, UVabsorbers, stabilizers, lubricants, plasticizers, anti-static agents,blowing agents, flame retardants, and combinations of the foregoing.

The following examples illustrate the methods of forming the disclosedpolymers.

EXAMPLES

Materials used in the following examples are listed in Table 1.

TABLE 1 ABBREVIATION DESCRIPTION SUPPLIER BPA Bisphenol A Sigma AldrichPET Poly(ethylene terephthalate); Dasani bottles; Tg = 67-81° C. PBTPoly(butylene terephthalate); Sigma Aldrich bottles; Tg = 37-51° C. PC-1Poly(bisphenol A carbonate); Sigma Aldrich Tg = 147° C. DMT DimethylTerephthalate Sigma Aldrich ArF Bis(4-Fluorophenyl)sulfone Sigma AldrichK2CO3 Potassium Carbonate Sigma Aldrich AP 4-Aminophenol Sigma AldrichTyr Tyramine Sigma Aldrich CHP N-Cyclohexyl-2-Pyrrolidone Sigma Aldrich

Herein, Mn is the number average molecular weight, Mw is the weightaverage molecular weight, and MW is the molecular weight of onemolecule.

Poly(bisphenol A carbonate) (PC-1) was used as received from Aldrich.Poly(ethylene terephthalate) (PET) flakes cut from waste Dasani bottleswere dissolved in tetrachloroethane and precipitated in methanol. Theprecipitate was filtered, dried in a vacuum oven 80° C., and powderedwith mortar and pestle prior to use. Poly(butylene terephthalate) (PBT)pellets purchased from Aldrichwere dissolved in tetrachloroethane andprecipitated in methanol. The precipitate was filtered, dried in avacuum oven at 80° C., and powdered with mortar and pestle prior to use.Dimethyl terephthalate (DMT) was powdered with mortar and pestle anddried overnight in a vacuum oven at 80° C. prior to use. Bisphenol A(BPA) was recrystallized from ethanol and dried in a vacuum ovenovernight at 80° C. prior to use. Bis(4-fluorophenyl)sulfone (ArF) wasrecrystallized from ethanol and dried in a vacuum oven overnight at 80°C. prior to use. Potassium carbonate (K₂CO₃) was ground with a mortarand pestle and dried in a vacuum oven at 80° C. prior to use.4-Aminophenol was opened in a glovebox and used as received from SigmaAldrich. Tyramine was opened in a glovebox and used as received fromSigma Aldrich.

d₆-DMSO and CDCl₃ were purchased from Cambridge Isotope Laboratories(CIL) and used as received. ¹H NMR spectra were recorded on a BrukerAvance 400 spectrometer (400 MHz). Chemical shifts are reported in ppmfrom tetramethylsilane with the solvent resonance as the internalstandard (CDCl₃: delta 7.26 ppm; d₆-DMSO: delta 2.50 ppm). Infrared (IR)spectra were recorded on a Thermo Nicolet Nexus 670 FT-IR Alphaspectrophotometer using a Nicolet OMNI-Sampler ATR Smart-Accessory,ν_(max) in cm⁻¹. Gel permeation chromatography (GPC) was performed inTHF or DMF using a Waters system equipped with four 5 micrometer Waterscolumns (300 mm×7.7 mm) connected in series with an increasing pore size(100, 1000, 10⁵, 10⁶ Å), a Waters 410 differential refractometer, and a996 photodiode array detector. The system was calibrated withpolystyrene standards.

Polymer Preparations

In the following examples, E′, E″, Z′, and Z″ are independent polymerchain end groups. E′ and E″ of PET, PBT and PC-1 are residues of thediol used to prepare these materials. End groups Z′ and Z″ of thepolymer products can be hydrogen (H), hydroxy (OH), fluoride (F),hydroxyethyleneoxy, hydroxybutyleneoxy, methoxy, and residue of BPA, andso on. Structures enclosed in parentheses within the square bracketsrepresent a repeating unit. Vertical stacking of the repeat units withinthe square brackets indicates a random distribution of the repeat unitswithin the polymer chain.

EXAMPLE 1 Preparation of P-1 from DMT Having 10 Mole % Amide ContainingRepeat Units (n′/(m′+n′)×100%=10%)

Tyramine (Tyr, 0.0275 g, 0.200 mmol, 0.2 equivalents), dimethylterephthalate (DMT, 0.0194 g, 0.100 mmol, 0.1 equivalents), bisphenol A(BPA, 0.205 g, 0.900 mmol, 0.9 equivalents), bis(4-fluorophenyl)sulfone(ArF, 0.254 g, 1.0 mmol, 1.0 equivalents), potassium carbonate (0.150,0.105 mmol, 1.05 equivalents), and N-cyclohexyl-2-pyrrolidone (CHP, 3.0g) were weighed into a 2 Dram vial in a glovebox equipped with stirbar.The solids concentration was 22 wt % based on total weight of themixture. The vial was capped and removed from the glovebox. A septum wasattached to the vial and the vial was sealed with TEFLON tape andelectrical tape. A nitrogen inlet needle and an exit needle wereinserted into the septum to allow the solution to slowly concentrate atelevated temperature. The reaction was heated at 190° C. for 18 hoursand allowed to cool. Methylene chloride (5 mL) was added to dissolve thecrude polymer. The polymer solution was clear and viscous. The polymerwas precipitated by addition of 15 mL of benchtop methanol at roomtemperature. The precipitate was filtered and dried in a vacuum ovenovernight at 80° C. to yield 0.415 g of an off-white powder P-1 (90%yield); n′/(m′+n′)×100%=10%. That is, the copolymer contained about 10mole % of the amide-sulfone repeat unit having the subscript n′, andabout 90 mole % of the BPA-sulfone repeat unit having the subscript m′.Mn =11868, Mw=15,750, PDI=1.327. FIG. 1 is a ¹H NMR spectrum of theproduct.

EXAMPLE 2 Preparation of P-1 from PBT Having 10 Mole % Amide ContainingRepeat Units (n′/(m′+n′)×100%=10%)

Tyramine (Tyr, 0.0275 g, 0.200 mmol, 0.2 equivalents), poly(butyleneterephthalate) (PBT, 0.0192 g, 0.100 mmol, 0.1 equivalents, Mn=38000,n=172), bisphenol A (BPA, 0.205 g, 0.900 mmol, 0.9 equivalents),bis(4-fluorophenyl)sulfone (ArF, 0.254 g, 1.0 mmol, 1.0 equivalents),potassium carbonate (0.150 g, 0.105 mmol, 1.05 equivalents), and CHP(3.0 g) were weighed into a 2 Dram vial in the glovebox equipped withstirbar. The solids concentration was 22 wt % based on total weight ofthe mixture. The vial was capped and removed from the glovebox. A septumwas attached to the vial and the vial was sealed with TEFLON tape andelectrical tape. A nitrogen inlet needle and an exit needle wereinserted into the septum to allow the solution to slowly concentrate atelevated temperature. The reaction was heated at 190° C. for 41 hoursand allowed to cool. Methylene chloride (5 mL) was added to dissolve thecrude polymer. The polymer solution was clear and viscous. The polymerwas precipitated by addition of 15 mL of benchtop methanol at roomtemperature. The precipitate was filtered and dried in a vacuum ovenovernight at 30° C. to yield 0.245 g of an off-white powder P-1 (57%yield; n′/(m′+n′)×100%=10%). Mn=71,928, Mw=129,552, PDI=1.80. FIG. 2 isa ¹H NMR spectrum of the product. The higher molecular weight polymerformed in Example 2 has limited solubility in DMSO, and therefore thesolvent signals of FIG. 2 are more intense compared to the signals ofFIG. 1.

EXAMPLE 3 Preparation of P-2 from Poly(Bisphenol A Carbonate) (PC-1)

Poly(bisphenol A carbonate) (PC-1, 0.272 g, 0.200 mmol, 0.1 equivalents,Mw 45000, n=175), bis(4-fluorophenyl)sulfone (ArF, 0.254 g, 1.0 mmol,1.0 equivalents), potassium carbonate (0.150 g, 0.105 mmol, 1.05equivalents), and CHP (3.0 g) were weighed into a 2 Dram vial in theglovebox equipped with stirbar. The solids concentration was 18 wt %based on total weight of the mixture. The vial was capped and removedfrom the glovebox. A septum was attached to the vial and the vial wassealed with TEFLON tape and electrical tape. A nitrogen inlet needle andan exit needle were inserted into the septum to allow the solution toslowly concentrate at elevated temperature. The reaction was heated at190° C. for 18 hours and allowed to cool. Methylene chloride (5 mL) wasadded to dissolve the crude polymer. The polymer solution was clear andviscous. The polymer was precipitated by addition of 15 mL of benchtopmethanol at room temperature. The precipitate was filtered and dried ina vacuum oven overnight at 80° C. to yield 0.373 g of an off-whitepowder (94% yield). IR (thin film), ν_(max) in cm⁻¹: 3066 (w), 2967 (m),2872 (w), 1586 (s), 1502 (s), 1488 (s), 1323 (m), 1294 (m), 1244 (s),1169 (s), 1151 (s). Mn=7644, Mw=12450, PDI=1.63, m′=17. FIG. 3 is a ¹HNMR spectrum of the product.

EXAMPLE 4 Attempted Preparation of P-3 from PET Having 50 Mole % AmideContaining Repeat Units (n′/(m′+n′)×100%=50%)

Tyramine (Tyr, 0.137 g, 1.00 mmol, 1.0 equivalents), poly(ethyleneterephthalate) (PET, 0.0821 g, 0.500 mmol, 0.5 equivalents, Mn 40000,n=206), bisphenol A (BPA, 0.114 g, 0.500 mmol, 0.5 equivalents),bis(4-fluorophenyl)sulfone (ArF, 0.254 g, 1.0 mmol, 1.0 equivalents),potassium carbonate (0.150 g, 0.105 mmol, 1.05 equivalents), and CHP(3.0 g) were weighed into a 2 Dram vial in the glovebox equipped withstirbar. The solids concentration was 20 wt % based on total weight ofthe mixture. The vial was capped and removed from the glovebox. A septumwas attached to the vial and the vial was sealed with TEFLON tape andelectrical tape. A nitrogen inlet needle and an exit needle wereinserted into the septum to allow the solution to slowly concentrate atelevated temperature. The reaction was heated at 190° C. for 44 hoursand allowed to cool. Methylene chloride (5 mL) was added to dissolve thecrude polymer. The polymer solution was clear and viscous. The polymerP-3 was precipitated by addition of 15 mL of benchtop methanol at roomtemperature. GPC analysis was performed in DMF eluent, however, due tothe difficulty in filtering, the reported average molecular weight ofthe soluble polymer is likely lower than the overall molecular weight ofthe sample. For P-3, n′/(m′+n′)×100%=50%. No other characterization ofthe polymer was obtained.

When the amount of the amide-sulfone repeat unit in the product polymerswas 50 mole % or higher, the product polymers were difficult to processdue to low solubility. Therefore, copolymers were prepared containing 10mole % to about 30 mole % of the amide-sulfone repeat unit and about 90mole % to about 70 mole % of a BPA-sulfone repeat unit, which served asa diluent.

Example 5 Attempted Preparation of P-3 from DMT Having 50% Amide Groups(n′/(m′+n′)×100%=50%)

Tyramine (0.137 g, 1.0 mmol, 1.0 equivalents), dimethyl terephthalate(DMT, 0.097 g, 0.500 mmol, 0.5 equivalents), bisphenol A (0.114 g, 0.5mmol, 0.5 equivalents), bis(4-fluorophenyl)sulfone (ArF, 0.254 g, 1.0mmol, 1.0 equivalents), potassium carbonate (0.150 g, 0.105 mmol, 1.05equivalents), and CHP (3.0 g) were weighed into a 2 Dram vial in theglovebox equipped with stirbar. The solids concentration was 20 wt %based on total weight of the mixture. The vial was capped and removedfrom the glovebox. A septum was attached to the vial and the vial wassealed with TEFLON tape and electrical tape. A nitrogen inlet needle andan exit needle were inserted into the septum to allow the solution toslowly concentrate at elevated temperature. The reaction was heated at190° C. for 44 hours. The polymer was not isolated.

EXAMPLE 6 (COMPARATIVE) Preparation of P-4

4-Aminophenol (AP, 0.0275 g, 0.200 mmol, 0.2 equivalents), poly(ethyleneterephthalate) (PET, 0.0161 g, 0.200 mmol, 0.1 equivalents.), bisphenolA (BPA, 0.205 g, 0.900 mmol, 0.9 equivalents),Bis(4-fluorophenyl)sulfone (ArF, 0.254 g, 1.0 mmol, 1.0 equivalents),potassium carbonate (0.150 g, 0.105 mmol, 1.05 equivalents), and CHP(3.0 g) were weighed into a 2 Dram vial in the glovebox equipped withstirbar. The solids concentration was 18 wt % based on total weight ofthe mixture. The vial was capped and removed from the glovebox. A septumwas attached to the vial and the vial was sealed with TEFLON tape andelectrical tape. A nitrogen inlet needle and an exit needle wereinserted into the septum to allow the solution to slowly concentrate atelevated temperature. The reaction was heated at 190° C. for 18 hoursand allowed to cool. Methylene chloride (5 mL) was added to dissolve thecrude polymer. The polymer solution was clear and viscous. The polymerwas precipitated by addition of 15 mL of benchtop methanol at roomtemperature. The precipitate was filtered and dried in a vacuum ovenovernight at 80° C. to yield 0.436 g of an off-white powder (99% yield,containing unreacted AP). Mn=7380 Mw=11341, PDI=1.53, m′˜16. IR analysisshowed no amide bonds. The AP did not appear to react at all. FIG. 4 isa ¹H NMR spectrum of the crude product mixture containing P-4. Theproduct structure is believed to be a BPA-poly aryl ether sulfonewithout amide functionality. FIG. 5 is a ¹H NMR spectrum of the purifiedpoly(arylene ether sulfone) product P-4.

EXAMPLE 7 (COMPARATIVE)

Attempted reaction of AP with PBT. The procedure of Example 6 wasrepeated using PBT. As before, no amide bonds were detected in thepolymer produced, indicating the AP was not incorporated. FIG. 6 is a ¹HNMR spectrum of the crude product mixture. FIG. 7 is a ¹H NMR spectrumof the isolated product.

Table 2 summarizes Examples 1 to 7. Number average molecular weights(Mn) and weight average molecular weight (Mw) were determined by gelpermeation chromatography (GPC) using dimethyl formamide (DMF). Polymerswere not fully soluble (presumably due to amide functionality),therefore the reported molecular weights are likely lower than actual.

TABLE 2 Reactants Time Temp Yield Mn Mw PDI Ex. (equivalents) Solvent(h) (° C.) (%) (eluent) (eluent) (eluent) 1 DMT (0.1), CHP 18 190 9011,475 17,925 1.56 Tyr (0.2), (THF) (THF) (THF) ArF (1.0), BPA (0.9),K₂CO₃ (1.05) 2 PBT (0.1), CHP 41 190 57 55,866 94,031 1.68 Tyr (0.2),(THF) (THF) (THF) ArF (1.0), BPA (0.9), K₂CO₃ (1.05) 3 PC-1 (1.0), CHP18 190 94 8,718 12,613 1.45 ArF (1.0), (THF) (THF) (THF) K₂CO₃ (1.05) 4PET (0.5), CHP 44 190 ND ND ND ND Tyr (1.0), ArF (1.0), BPA (0.5), K₂CO₃(1.05) 5 DMT (0.5), CHP 44 190 ND ND ND ND Tyr (1.0), ArF (1.0), BPA(0.5), K₂CO₃ (1.05) 6 PET (0.1), CHP 23 190 No AP 7,380 11,341 1.54(comp) AP (0.2), incorporated ArF (1.0), BPA (0.9), K₂CO₃ (1.05) 7 PBT(0.1), CHP 23 190 No AP 6,679 10,651 1.59 (comp) AP (0.2), incorporatedArF (1.0), BPA (0.9), K₂CO₃ (1.05) ND = not determined

Spectroscopic and thermal data for Examples 1-7 are listed in Table 3.Glass transition temperature (Tg) was measured by differential scanningcalorimetry (DSC). Examples 6 and 7, which used 4-aminophenol (AP),showed no amide peak by FT-IR. That is, AP did not react with PET andPBT to form a diol-diamide intermediate.

TABLE 3 Tg IR carbonyl peaks Example. (° C.) (cm⁻¹) (intensity) 1 1681723 (medium), 1654 (medium) 2 217 1717 (weak), 1675 (strong) 4 5 6(comp) 169 1721 (medium) 7 (comp) 171 1717 (medium

EXAMPLE 8 Single Pot, 4-Component Reaction for the Synthesis ofAmide-containing Poly(Aryl Ether Sulfone) from AP and DMT

4-Aminophenol (AP, 0.0654 g, 0.600 mmol, 0.6 equivalents), dimethylterephthalate (DMT, 0.0582 g, 0.300 mmol, 0.3 equivalents), bisphenol A(BPA, 0.205 g, 0.900 mmol, 0.9 equivalents), bis(4-fluorophenyl)sulfone(ArF, 0.254 g, 1.0 mmol, 1.0 equivalents), potassium carbonate (0.138 g,1.00 mmol, 1.00 equivalents), and DMF (2.02 mL) were weighed into a 2Dram vial in the glovebox equipped with stirbar. The solidsconcentration was 25 wt % based on total weight of the mixture. The vialwas capped and removed from the glovebox. A septum was attached to thevial and the vial was sealed with TEFLON tape and electrical tape. Anitrogen inlet needle and an exit needle were inserted into the septumto allow the solution to slowly concentrate at elevated temperature. Thereaction was followed by ¹H NMR. 4-Aminophenol was consumed first within2.5 hours in the reaction with DMT. New ¹H NMR signals were seencorresponding to a new amide-containing bisphenol intermediate I-1. FIG.8 is a ¹H NMR spectrum of the reaction mixture containing I-1. Thesedata suggested that amidation was kinetically favored over reaction ofBPA with diaryl sulfone ArF, and as a result, both requisite bisphenolmonomers (I-1 and BPA) were present in the reaction solution prior tothe ether-forming aromatic nucleophilic substitution reaction (S_(N)Ar)resulting in the product polymer. The reaction was heated at 150° C. for18 hours and allowed to cool. The polymer was precipitated by additionof 15 mL of benchtop methanol at room temperature. The precipitate wasfiltered and dried in a vacuum oven overnight at 80° C. to yield 0.251 gof an off-white powder (56% yield).

The purified poly(arylene ether amide sulfone) P-8 was characterized by¹³C (FIG. 9), ¹H NMR (FIG. 10), and GPC (FIG. 11, n′/m′+n′×100%=30%,Mn=9371, Mw=16882, PDI=1.80). The product was identified as the desiredpoly(arylene ether amide sulfone) P-8 containing both amide and etherfunctionality.

P-8 was also prepared from separately synthesized I-1 as describedbelow.

EXAMPLE 9 Preparation of I-1 Monomer

Triethylamine (TEA, 5.4 mL, 40 mmol), tetrahydrofuran (THF, 100 mL), andof p-aminophenol (AP, 4.36 g, 40 mmol) were added to a 250-mL flask.CHCl₃ containing terephthaloyl dichloride (4.06 g, 20 mmol) was addeddropwise to the solution with vigorous stirring at ambient temperature.The reaction was filtered to remove THF and CHCl₃. The filter cake waswashed with a large amount of water and the solid material then vacuumdried to yield 6.2 grams of pureN₁,N₄-bis(4-hydroxyphenyl)terephthalamide monomer (I-1). FIG. 12, ¹HNMR: (400 MHz, d₆-DMSO): δ 10.18 (s, 2H), 9.33 (bs, 2H), 8.06 (s, 4H),7.56 (d, J=8.2 Hz, 2H), 6.77 (d, J=8.2 Hz, 2H); ¹³C NMR (100 MHz,d₆-DMSO): δ 164.3, 153.9, 137.5, 130.5, 127.6, 122.4, 115.2.

EXAMPLE 10 Preparation of P-8 from I-1

To a 250-ml three-neck round bottom flask equipped with a stir bar, aDean-Stark trap and a condenser, bis-amide monomer I-1 (0.547 g, 15.700mmol), BPA (1.433 g, 6.280 mmol), ArF (2.000 g, 78.600 mmol), and K₂CO₃(3.250 g, 23.580 mmol) were added. To this mixture NMP (15 ml) andtoluene (65 ml) were added and the reaction was stirred for 10 minutesunder a nitrogen atmosphere. The reaction setup was then placed in anoil-bath and the internal reaction temperature was set to 125° C. for 18hours to azeotropically remove water from the reaction mixture. Thereaction temperature was slowly increased to 170° C. over a period offour hours to completely remove the toluene. The reaction was then heldat 170° C. for three hours at which point a dramatic increase in theviscosity was observed. The reaction was cooled to about 80° C. and wasprecipitated in deionized water. The polymer was stirred in water at 60°C. overnight followed, filtered, and stirred in methanol for four hoursat 50° C. to ensure complete removal of NMP and water. The resultingpolymer was filtered and dried under vacuum at 70° C. for 24 hours (FIG.13, ¹H NMR spectrum). ¹H NMR (400 MHz, d₆-DMSO) δ: 1.60 (CH₃—C—CH₃,BPA), δ: (6.6-6.7, NH—Ar), δ: 7.01 (Ar, BPA), δ: 7.25, 7.80 (SO₂—Ar), δ:8.08, δ: 10.45 (C═O—NH—Ar). T_(g) (DSC)=224° C. M_(n)=62.1K,M_(w)=132.8K, PDI=2.13, n′/m′+n′×100%=30%, m′=90, n′=38.

Notably, the data obtained using the 4-component one-pot procedure ofExample 8 were in agreement with data from Example 10 in which P-8 wassynthesized from purified I-1 monomer (compare FIG. 13 with FIG. 10).Amide peaks can move depending on concentration of solvent. Theremaining peaks that are unaffected by NMR conditions match.

In conclusion, complex random co-polymers were formed in one reactionvessel that involve multiple condensation reactions. This methodprovides access to a wide range of new, multi-component polymers as wellas increased efficiency in the manufacture of current polymers of highcommercial value.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of the invention. Asused herein, the singular forms “a”, “an” and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise. It will be further understood that the terms “comprises”and/or “comprising,” when used in this specification, specify thepresence of stated features, integers, steps, operations, elements,and/or components, but do not preclude the presence or addition of oneor more other features, integers, steps, operations, elements,components, and/or groups thereof. When a range is used to express apossible value using two numerical limits X and Y (e.g., a concentrationof X ppm to Y ppm), unless otherwise stated the value can be X, Y, orany number between X and Y.

The description of the present invention has been presented for purposesof illustration and description, but is not intended to be exhaustive orlimited to the invention in the form disclosed. Many modifications andvariations will be apparent to those of ordinary skill in the artwithout departing from the scope and spirit of the invention. Theembodiments were chosen and described in order to best explain theprinciples of the invention and their practical application, and toenable others of ordinary skill in the art to understand the invention.

What is claimed is:
 1. A method, comprising: forming a mixturecomprising i) a polycarbonate having a repeat unit of formula (2):

wherein L^(b) is a divalent radical comprising 2 or more carbons, ii) abis-aryl sulfone of formula (4):

wherein each E′ is an independent monovalent radical selected from thegroup consisting of hydrogen and electron withdrawing groups, and eachX′ is an independent monovalent leaving group, iii) a base comprising acarbonate dianion (CO₃ ⁻²), wherein the mixture contains between 0.05mole and 1.0 mole of the base per mole of the bis-aryl sulfone, and iv)a solvent; and heating the mixture at a reaction temperature of about150° C. to about 250° C. while removing any volatile organic byproductsfrom the heated mixture using a stream of inert gas, thereby forming apoly(ether sulfone) (PES).
 2. The method of claim 1, wherein each X′ isselected from the group consisting of fluoride, chloride, bromide,iodide, trifluoromethoxy (*—OCF₃), trichloromethoxy (*—OCCl₃), andtrifluoromethanesulfonyl (*—OS(═O)₂CF₃).
 3. The method of claim 1,wherein each X′ is fluoride.
 4. The method of claim 1, wherein at leastone X′ is chloride.
 5. The method of claim 1, wherein at least one X′ isbromide.
 6. The method of claim 1, wherein at least one X′ is iodide. 7.The method of claim 1, wherein each E′ is hydrogen.
 8. The method ofclaim 1, wherein each E′ is an electron withdrawing group selected fromthe group consisting of nitro (*—NO₂), cyano (*—CN), trifluoromethyl(*—CF₃), trichloromethyl (*—CCl₃), and alkylsulfones (*—S(═O)₂R^(a)),wherein Ra is an alkyl or aryl group comprising 1 to 10 carbons.
 9. Themethod of claim 1, wherein at least one E′ is nitro.
 10. The method ofclaim 1, wherein at least one E′ is trifluoromethyl.
 11. The method ofclaim 1, wherein at least one E′ is trichloromethyl.
 12. The method ofclaim 1, wherein at least one E′ is an alkylsulfone (*—S(═O)₂R^(a)),wherein R^(a) is an alkyl or aryl group comprising 1 to 10 carbons. 13.The method of claim 1, wherein L^(b) comprises at least one aromaticring.
 14. The method of claim 1, wherein the polycarbonate ispost-consumer poly(bisphenol A carbonate).
 15. The method of claim 1,wherein the base is K₂CO₃.
 16. The method of claim 1, wherein the PEShas a number average molecular weight (Mn) in the range of about 1000 toabout 1,000,000.
 17. The method of claim 1, wherein the PES has astructure in accordance with formula (5):

wherein m is a positive number greater than or equal to 1, each L^(b) isan independent divalent linking group comprising 2 or more carbons, eachE′ is an independent monovalent radical selected from the groupconsisting of hydrogen and electron withdrawing groups, Y′ is a firstpolymer chain end group, and Y″ is a second polymer chain end group. 18.The method of claim 1, wherein the PES has a structure in accordancewith formula (6):

wherein m is a positive number greater than or equal to 1, R′ is amonovalent radical selected from the group consisting of hydrogen,halides, and groups comprising 1 or more carbons, R″ is a monovalentradical selected from the group consisting of hydrogen, halides, andgroups comprising 1 or more carbons, each E′ is an independentmonovalent radical selected from the group consisting of hydrogen andelectron withdrawing groups, Y′ is a first polymer chain end group, andY″ is a second polymer chain end group.
 19. The method of claim 18,wherein R′ and R″ are methyl.
 20. The method of claim 1, wherein thesolvent is N -cyclohexyl-2-pyrrolidinone.